biostudies-literatureZhu JNatural Science Foundation of Jiangsu Province (Jiangsu Provincial Natural Science Foundation)Natural Science Foundation of Shandong Province (Shandong Provincial Natural Science Foundation)Natural Science Foundation of Shandong ProvinceNational Natural Science Foundation of ChinaNational Natural Science Foundation of China (National Science Foundation of China)Taishan Scholar Foundation of Shandong ProvinceNatural Science Foundation of Jiangsu Province1565https://www.ebi.ac.uk/biostudies/studies/S-EPMC10879110biostudies-literatureUnknown15(1)Cu-oxide-based catalysts are promising for CO₂ electroreduction (CO₂RR) to CH₄, but suffer from inevitable reduction (to metallic Cu) and uncontrollable structural collapse. Here we report Cu-based rock-salt-ordered double perovskite oxides with superexchange-stabilized long-distance Cu sites for efficient and stable CO₂-to-CH₄ conversion. For the proof-of-concept catalyst of Sr₂CuWO₆, its corner-linked CuO₆ and WO₆ octahedral motifs alternate in all three crystallographic dimensions, creating sufficiently long Cu-Cu distances (at least 5.4 Å) and introducing marked superexchange interaction mainly manifested by O-anion-mediated electron transfer (from Cu to W sites). In CO₂RR, the Sr₂CuWO₆ exhibits significant improvements (up to 14.1 folds) in activity and selectivity for CH₄, together with well boosted stability, relative to a physical-mixture counterpart of CuO/WO₃. Moreover, the Sr₂CuWO₆ is the most effective Cu-based-perovskite catalyst for CO₂ methanation, achieving a remarkable selectivity of 73.1% at 400 mA cm^-2 for CH₄. Our experiments and theoretical calculations highlight the long Cu-Cu distances promoting *CO hydrogenation and the superexchange interaction stabilizing Cu sites as responsible for the superb performance.Nature communicationsSuperexchange-stabilized long-distance Cu sites in rock-salt-ordered double perovskite oxides for CO₂ electromethanation.PMC1087911052102258BK20210447tsqn202306309ZR2023YQ012Zhu JChen ZZhang ZZhu YZhang YTian XJiang HHuang MWang XBai XfalseSuperexchange-stabilized long-distance Cu sites in rock-salt-ordered double perovskite oxides for CO₂ electromethanation.Cu-oxide-based catalysts are promising for CO₂ electroreduction (CO₂RR) to CH₄, but suffer from inevitable reduction (to metallic Cu) and uncontrollable structural collapse. Here we report Cu-based rock-salt-ordered double perovskite oxides with superexchange-stabilized long-distance Cu sites for efficient and stable CO₂-to-CH₄ conversion. For the proof-of-concept catalyst of Sr₂CuWO₆, its corner-linked CuO₆ and WO₆ octahedral motifs alternate in all three crystallographic dimensions, creating sufficiently long Cu-Cu distances (at least 5.4 Å) and introducing marked superexchange interaction mainly manifested by O-anion-mediated electron transfer (from Cu to W sites). In CO₂RR, the Sr₂CuWO₆ exhibits significant improvements (up to 14.1 folds) in activity and selectivity for CH₄, together with well boosted stability, relative to a physical-mixture counterpart of CuO/WO₃. Moreover, the Sr₂CuWO₆ is the most effective Cu-based-perovskite catalyst for CO₂ methanation, achieving a remarkable selectivity of 73.1% at 400 mA cm^-2 for CH₄. Our experiments and theoretical calculations highlight the long Cu-Cu distances promoting *CO hydrogenation and the superexchange interaction stabilizing Cu sites as responsible for the superb performance.2024-01-01T00:00:00Z2024 Feb2025-04-05T00:31:15.673Z2025-04-05T00:31:15.673ZS-EPMC108791103837862910.1038/s41467-024-45747-5